CN116041212A - 一种二氟烯烃醚和肟醚类衍生物的制备及应用 - Google Patents

一种二氟烯烃醚和肟醚类衍生物的制备及应用 Download PDF

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CN116041212A
CN116041212A CN202310055132.3A CN202310055132A CN116041212A CN 116041212 A CN116041212 A CN 116041212A CN 202310055132 A CN202310055132 A CN 202310055132A CN 116041212 A CN116041212 A CN 116041212A
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dichlorophenyl
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李亚辉
李绍晨
张翅鹰
田青强
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Anhui Agricultural University AHAU
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Abstract

本发明涉及系列结构新颖的二氟烯醚和肟醚类衍生物的制备及应用。该系列二氟烯醚和肟醚类衍生物的结构通式如式（I）和（II）所示，经研究发现本发明公开的二氟烯烃醚和肟醚类衍生物对小菜蛾、玉米螟、草地贪夜蛾和朱砂叶螨等常见危害严重的农业害虫/螨具有较好的生物活性，故可作为杀虫/螨剂候选物用于高效、低毒、环保的新型杀虫剂研发。

Description

一种二氟烯烃醚和肟醚类衍生物的制备及应用
技术领域
本发明属于农药技术领域，涉及一种二氟烯烃醚和肟醚类衍生物在制备新型高效杀虫剂/杀螨剂中的应用。
背景技术
肟醚衍生物在农药应用方面是一类重要的活性化合物。有关肟醚活性化合物国内外已有大量报道同时也有许多商品问世。例如，唑螨酯(Fenpyroximate)是一类作用于NADH-辅酶Q还原酶的杀虫/螨剂，主要用于防治小菜蛾、稻飞虱和各种螨类。由于肟醚类化合物具有很好的杀虫(Chin.J.Org.Chem.2017,37,3155)、杀螨(农药,2005,43,196-200)、杀菌(Chin.J.Org.Chem.2017,37,1537)、除草(Chem.Res.Chin.Univ.2016,32,195)等生物活性，且大多具有高效、低毒、低残留等优点，因此在当前新农药创制中肟醚结构仍然是常被选用的有效活性基团。
氟原子拥有最强的电负性和独特的电子及空间位阻效应，含氟的化合物往往显示出与常规化合物不同的特征和规律，因此具有独特的学术研究价值。近年来，新研发的农药分子有50％以上至少含有一个氟原子。含氟农药已经成为当今新农药创制的主题。
二氟烯醚由于其结构的特殊性，在农业化学有其独特的价值。例如在抗病毒，杀虫和除草。同时这些化合物通常具有高效低毒在环境中容易降解等特点，所以在农药的研究和开发中，含有二氟烯醚结构的化合物显示出越来越重要的作用。
发明内容
本发明的目的在于提供一种具有高杀虫活性的二氟烯烃醚和肟醚类衍生物制备及应用。
为此，本发明提供的二氟烯烃醚和肟醚类衍生物化学结构通式如式(I)和(II)所示：
Figure BDA0004060289660000011
式(I)中：Ar独立地选自苯基、苄基、吡啶基、吡唑基、吡咯基、呋喃基、噻唑基、苯并吡咯基中的一个或多个；R独立地选自苯基、苄基、吡啶基、吡唑基、吡咯基、呋喃基、噻唑基、苯并吡咯基中的一个或多个；
式(II)中：R1独立地选自腈基、硝基、任意取代或未取代的烷基、任意取代或未取代的烷氧基、任意取代或未取代的芳基、任意取代或未取代的杂芳基中的一个或多个；R2独立地选自腈基、硝基、任意取代或未取代的烷基、任意取代或未取代的烷氧基、任意取代或未取代的芳基、任意取代或未取代的杂芳基中的一个或多个；R3独立地选自任意取代或未取代的烷基、任意取代或未取代的烷氧基、任意取代或未取代的芳基、任意取代或未取代的杂芳基中的一个或多个。
优选地，Ar为独立地选自任意取代或未取代的C5-C6芳基、任意取代或未取代的C5-C6杂芳基中的一个或多个；R为独立地选自任意取代或未取代的C5-C6芳基、任意取代或未取代的C5-C6杂芳基中的一个或多个；R1独立地选自腈基、硝基、任意取代或未取代的C1-C6烷基、任意取代或未取代的C1-C6烷氧基、任意取代或未取代的C5-C6芳基、任意取代或未取代的C5-C6杂芳基中的一个或多个；R2独立地选自腈基、硝基、任意取代或未取代的C1-C6烷基、任意取代或未取代的C1-C6烷氧基、任意取代或未取代的C5-C6芳基、任意取代或未取代的C5-C6杂芳基中的一个或多个；R3独立地选自任意取代或未取代的C1-C6烷基、任意取代或未取代的C1-C6烷氧基、任意取代或未取代的C5-C6芳基、任意取代或未取代的C5-C6杂芳基中的一个或多个。
更优选地，Ar为独立地选自苯基、吡啶基、吡唑基、吡咯基、呋喃基、噻唑基、苯并吡咯基中的一个或多个；R为独立地选自苯基、吡啶基、吡唑基、吡咯基、呋喃基、噻唑基、苯并吡咯基中的一个或多个；R1独立地选自甲基、乙基、正丙基、正丁基、仲丁基、异丁基、苯基、苄基、吡啶基、吡唑基、吡咯基、呋喃基、噻唑基、苯并吡咯基、哒嗪、嘧啶、吡嗪、-CN、-NO2、-CH2CN、-CH2CH2CN、CH2CH2CN、CHCNCH3、CH2CH2CH2CN、CH2CHCNCH3、CHCNCH2CH3、
Figure BDA0004060289660000021
R2独立地选自甲基、乙基、正丙基、正丁基、仲丁基、异丁基、苯基、苄基、吡啶基、吡唑基、吡咯基、呋喃基、噻唑基、苯并吡咯基、哒嗪、嘧啶、吡嗪、-CN、-NO2、-CH2CN、-CH2CH2CN、CH2CH2CN、CHCNCH3、CH2CH2CH2CN、CH2CHCNCH3、CHCNCH2CH3、
Figure BDA0004060289660000022
R3独立地选自甲基、乙基、正丙基、正丁基、仲丁基、异丁基、苯基、苄基、吡啶基、吡唑基、吡咯基、呋喃基、噻唑基、苯并吡咯基中的一个或多个。
本发明所述的二氟烯烃肟醚类衍生物的制备路线为：
Figure BDA0004060289660000031
可选的，步骤(1)反应在乙醇(EtOH)和水(H2O)中进行，同时加入盐酸羟胺和醋酸钠，反应温度为80℃。
可选的，所述的酮类化合物
Figure BDA0004060289660000032
选自4-溴苯乙酮、4-碘苯乙酮、2,6-二氟苯乙酮、2-溴,4-氟苯乙酮、3-三氟甲基苯乙酮、3-甲基-4氟苯乙酮、2-呋喃基甲基甲酮、2-萘乙酮、3,4-(亚甲基二氧)苯乙酮、2-乙酰基-1-甲基吡咯、3-苯氧基苯乙酮、2-噻吩基甲基甲酮、4-二氢色原酮的一种。
可选的，步骤(2)反应在无水N,N-二甲基甲酰胺(DMF)中进行，同时加入碳酸铯，且存在氮气保护，反应温度为90℃。
可选的，步骤(2)所述的化合物
Figure BDA0004060289660000033
为1,3-二氯-5-(1-三氟甲基-乙烯基)苯。
本发明所述的二氟烯烃醚类衍生物的制备路线为:
Figure BDA0004060289660000034
无水N,N-二甲基甲酰胺(DMF)中进行，同时加入碳酸铯，反应温度为30℃。
本发明的二氟烯烃醚和肟醚类衍生物用于制备杀虫剂的应用。并且本发明的二氟烯烃醚和肟醚类衍生物用于制备杀螨剂的应用。所述害虫包括农业上常见的鳞翅目类害虫，比如常见的小菜蛾、草地贪夜蛾、玉米螟等。所述的螨指农业常见的螨，例如的朱砂叶螨、二斑叶螨等。
有益效果：采用本发明的所提供的化合物，在0.5mg/mL浓度时化合物1-4，6-8，10-12和14对小菜蛾表现出100％致死率，化合物1，3，4，7，11，13，14对玉米螟表现出100％致死率，化合物7和14对草地贪夜蛾致死率为100％。
其中化合物7，12及14在10ug/mL时对小菜蛾致死率为100％；对玉米螟致死率为100％，80％及100％；对草地贪夜蛾致死率分别为100％，45％及100％。
二氟烯烃醚类化合物16-26在0.5mg/mL浓度下对朱砂叶螨杀虫活性大于80％。
附图说明
图1.化合物8的氢谱；
图2.化合物9的氢谱。
具体实施方式
除非有特殊说明，本文中的术语根据相关领域普通技术人员认识理解。
以下结合附图和实施例对本发明做进一步详细阐述。
鉴于二氟烯烃醚和肟醚类衍生物具有较好应用价值，申请人制备了二氟烯烃醚和肟醚类衍生物，并进行杀虫/螨活性研究；结果表明，该二氟烯烃醚和肟醚类衍生物具有显著的杀虫/螨活性，能够用于制备杀虫/螨剂。根据申请人所进行的资料检索，目前还未见文献报道。
以下是发明人给出的具体实施例。
实施例
实施例1：二氟烯烃肟醚类衍生物化合物1～15
一、产品：二氟烯烃肟醚类衍生物1～15(见表1，各化合物理化性质详见以下内容)
表1.本发明制备的二氟烯烃肟醚类衍生物1～15对应取代基及化合物结构式
Figure BDA0004060289660000041
Figure BDA0004060289660000051
Figure BDA0004060289660000061
实施例2：二氟烯烃醚类衍生物16～26
二、产品：二氟烯烃醚类衍生物16～26(见表2，各化合物理化性质详见以下内容)
表2.本发明制备的二氟烯烃醚类衍生物16～26对应取代基及化合物结构式
Figure BDA0004060289660000062
Figure BDA0004060289660000071
三、二氟烯烃肟醚类衍生物制备方法：
首先，在25mL反应管中加入不同取代基的酮类化合物(1.0eq)溶于75％EtOH水溶液中，后加入NH2OH·HCl(1.6eq)和CH3COONa(2.0eq)，在80℃下反应，TLC检测反应完全，反应温度降至室温，加入清水至不在有沉淀析出，抽滤，滤饼用清水洗涤，干燥，重结晶得到肟类化合物。然后纯化后的酮肟(1.0eq)、1,3-二氯-5-(1-三氟甲基-乙烯基)苯(1.5eq)和Cs2CO3(1.5eq)溶于DMF(2.0mL)中，在氮气环境下90℃反应12h，然后将混合物冷却至室温，加入饱和食盐水(15mL)，用乙酸乙酯(EtOAc)(30mL×3)萃取。合并有机相，无水Na2SO4干燥，过滤，真空浓缩，通过柱层析分离得到化合物1～13。
反应通式如下：
Figure BDA0004060289660000081
四、二氟烯烃醚类衍生物制备方法：
首先，在25mL反应管中加入不同取代基的酚类化合物(2.0eq)溶于(1.0eq)、1,3-二氯-5-(1-三氟甲基-乙烯基)苯(1.0eq)和Cs2CO3(2.0eq)溶于DMF(2.0mL)中，在氮气环境下30℃反应12h，反应结束后，加入饱和食盐水(15mL)，用乙酸乙酯(EtOAc)(30mL×3)萃取。合并有机相，无水Na2SO4干燥，过滤，真空浓缩，通过柱层析分离得到化合物16～26。
反应通式如下：
Figure BDA0004060289660000082
化合物1：(E)-1-(4-溴苯基)乙烷-1-酮-O-(2-(3，5-二氯苯基)-1，1-二氟烯丙基)肟
该化合物的理化性质如下：
无色油状物；产率为68％；该化合物的结构表征：1H NMR(600MHz,CDCl3)δ7.53(q,J＝8.7Hz,4H),7.38(d,J＝1.4Hz,2H),7.35(s,1H),6.05(s,1H),5.77(s,1H),2.24(s,3H).HRMS(ESI)calcd for C17H13BrCl2F2NO[M+H+]+:433.9520,found 433.9517.
化合物2：(E)-1-(4-碘苯基)乙烷-1-酮O-(2-(3，5-二氯苯基)-1，1-二氟烯丙基)肟
该化合物的理化性质如下：
无色油状物；产率为70％；该化合物的结构表征：1H NMR(600MHz,CDCl3)δ7.73(d,J＝8.5Hz,2H),7.39(dd,J＝9.1,4.9Hz,4H),7.34(s,1H),6.05(s,1H),5.77(s,1H),2.23(s,3H).HRMS(ESI)calcd for C17H13ICl2F2NO[M+H+]+:481.9381,found 481.9374.
化合物3：(E)-1-(2，6-二氟苯基)乙烷-1-酮O-(2-(3，5-二氯苯基)-1，1-二氟烯丙基)肟
该化合物的理化性质如下：
无色油状物；产率为72％；该化合物的结构表征：1H NMR(600MHz,CDCl3)δ7.38(s,2H),7.37–7.31(m,2H),6.94(t,J＝8.0Hz,2H),6.05(s,1H),5.75(s,1H),2.22(s,3H).HRMS(ESI)calcd for C17H11Cl2F4NO[M+H+]+:392.0226,found 392.0224.
化合物4：(E)-1-(2-溴-4-氟苯基)乙烷-1-酮O-(2-(3，5-二氯苯基)-1，1-二氟烯丙基)肟
该化合物的理化性质如下：
无色油状物；产率为70％；该化合物的结构表征：1H NMR(600MHz,CDCl3)δ7.39(s,2H),7.35(d,J＝12.5Hz,2H),7.29–7.26(m,1H),7.06(t,J＝8.2Hz,1H),6.05(s,1H),5.76(s,1H),2.23(s,3H).HRMS(ESI)calcd for C17H11Cl2F3NOBr[M+H+]+:451.9425,found451.9421.
化合物5：(E)-1-(3-三氟甲基)苯基乙烷-1-酮O-(2-(3，5-二氯苯基)-1，1-二氟烯丙基)肟
该化合物的理化性质如下：
无色油状物；产率为78％；该化合物的结构表征：1H NMR(600MHz,CDCl3)δ7.92–7.84(m,2H),7.69(d,J＝7.7Hz,1H),7.53(t,J＝7.8Hz,1H),7.39(s,2H),7.35(s,1H),6.07(s,1H),5.79(s,1H),2.30(s,3H).HRMS(ESI)calcd for C18H12Cl2F5NO[M+H+]+:424.0288,found424.0281
化合物6：1-(4-氟-3-甲基苯基)乙烷-1-酮O-(2-(3，5-二氯苯基)-1，1-二氟烯丙基)肟
该化合物的理化性质如下：
无色油状物；产率为80％；该化合物的结构表征：1H NMR(600MHz,CDCl3)δ7.52(d,J＝7.2Hz,1H),7.45(s,1H),7.39(s,2H),7.35(d,J＝1.4Hz,1H),7.01(t,J＝8.9Hz,1H),6.06(s,1H),5.77(s,1H),2.30(s,3H),2.24(s,3H).HRMS(ESI)calcd for C18H15Cl2F3NO[M+H+]+:388.0477,found 388.0472.
化合物7：(E)-1-(3-甲基-4-(1H-1,2,4-三唑-2-基)苯基)比1-1-O-(2-(3,5-二氯苯基)-1,1-二氟烯丙基)肟
该化合物的理化性质如下：黄色固体；产率为73％；该化合物的结构表征：1H NMR(600MHz,CDCl3)δ9.12(s,1H),8.37(s,1H),7.55(d,J＝7.2Hz,1H),7.43(s,1H),7.37(s,2H),7.33(d,J＝1.4Hz,1H),7.01(t,J＝8.9Hz,1H),6.05(s,1H),5.76(s,1H),2.30(s,3H),2.24(s,3H).HRMS(ESI)calcd for C20H16Cl2F2N4O[M+H+]+:437.0742,found 437.0730.
化合物8：(E)-1-呋喃-2-基)乙烷-1-酮O-(2-(3，5-二氯苯基)-1，1-二氟烯丙基)肟
该化合物的理化性质如下：
黄色固体；产率为82％；该化合物的结构表征：1H NMR(600MHz,CDCl3)δ7.52(s,1H),7.39(d,J＝1.3Hz,2H),7.34(d,J＝1.6Hz,1H),6.82(d,J＝3.3Hz,1H),6.47(dd,J＝3.2,1.7Hz,1H),6.06(s,1H),5.77(s,1H),2.19(s,3H).HRMS(ESI)calcd forC15H11Cl2F2NO2[M+H+]+:346.0207,found 346.0211.
化合物9：(E)-1-萘-2-基)乙烷-1-酮O-(2-(3，5-二氯苯基)-1，1-二氟烯丙基)肟该化合物的理化性质如下：
黄色固体；产率为76％；该化合物的结构表征：1H NMR(600MHz,cdcl3)δ8.07(s,1H),7.88(d,J＝8.0Hz,2H),7.84(d,J＝7.1Hz,2H),7.56–7.49(m,2H),7.43(s,2H),7.36(s,1H),6.09(s,1H),5.80(s,1H),2.39(s,3H).HRMS(ESI)calcd for C21H15Cl2F2NO[M+H+]+:406.0571,found 406.0563.
化合物10：(E)-1-萘-2-基)乙烷-1-酮O-(2-(3，5-二氯苯基)-1，1-二氟烯丙基)肟
该化合物的理化性质如下：
白色固体；产率为83％；该化合物的结构表征：1H NMR(600MHz,cdcl3)δ7.39(s,2H),7.34(s,1H),7.22(s,1H),7.15(d,J＝8.1Hz,1H),6.81(d,J＝8.1Hz,1H),6.05(s,1H),5.99(s,2H),5.76(s,1H),2.22(s,3H).HRMS(ESI)calcd for C18H13Cl2F2NO3[M+H+]+:400.0313,found 400.0311.
化合物11：(E)-1-(1-甲基-1h-吡咯-2-基)1-1-O-(2-(3,5-二氯苯基)-1,1-二氟烯丙基)肟
该化合物的理化性质如下：
黄色固体；产率为73％；该化合物的结构表征：1H NMR(600MHz,CDCl3)δ7.38(d,J＝1.4Hz,2H),7.33(s,1H),7.14(d,J＝6.4Hz,1H),6.62(d,J＝8.6Hz,1H),6.20(m,1H),6.04(s,1H),5.77(s,1H),2.24(s,3H).HRMS(ESI)calcd for C16H16Cl2F2N2O[M+H+]+:359.0524,found 359.0522.
化合物12：(E)-1-(4-苯氧基)1-1O-(2-(3,5-二氯苯基)-1,1-二氟烯丙基)肟
该化合物的理化性质如下：
无色液体；产率为72％；该化合物的结构表征：1H NMR(600MHz,CDCl3)δ7.87(d,J＝8.8Hz,2H),7.49(s,1H),7.42(d,J＝6.4Hz,2H),7.12-7.01(m,7H),6.04(s,1H),5.75(s,1H),2.24(s,3H).HRMS(ESI)calcd for C23H18Cl2F2NO2[M+H+]+:448.0677,found 448.0673.
化合物13：(E)-1-(噻吩-2-基)比1-1-O-(2-(3,5-二氯苯基)-1,1-二氟烯基)肟
无色液体；产率为58％；该化合物的结构表征：1H NMR(600MHz,CDCl3)δ7.52(m,3H),7.22(d,J＝7.4Hz,2H),7.12(t,J＝8.9Hz,1H),6.01(s,1H),5.73(s,1H),2.24(s,3H).HRMS(ESI)calcd for C23H19Cl2F2NO2[M+H+]+:361.9979,found 361.9972.
化合物14：(E)-N-(氰基甲基)-4-(1-(((2-(3,5-二氯苯基)-1,1-二氟烯丙基)肟)乙基)-2-甲基苯胺
该化合物的理化性质如下：
白色固体；产率为63％；该化合物的结构表征：1H NMR(600MHz,CDCl3)δ8.92(s,1H),8.02(d,J＝8.4Hz,1H),7.90(s,2H),7.39(d,J＝6.4Hz,2H),7.33(s,1H),6.04(s,1H),5.75(s,1H),2.24(s,3H).HRMS(ESI)calcd for C21H18Cl2F2N3O2[M+H+]+:452.0738,found452.0742.化合物16.1,3-二氯-5-(3,3-二氟-3-苯氧基丙-1-烯-2-基)苯
该化合物的理化性质如下：
无色油状物；收率为75％；该化合物的结构表征：1H NMR(600MHz,Chloroform-d)δ7.42(s,2H),7.38–7.33(m,3H),7.22(t,J＝7.4Hz,1H),7.18(d,J＝7.8Hz,2H),6.07(s,1H),5.74(s,1H)；HRMS(ESI)calcd for C16H11O3Cl2F2[M+HCOO]-:359.0048,found359.0047.
化合物17.4-((2-(3,5-二氯苯基)-1,1-二氟烯丙基)氧基)-1,2-二甲基苯
该化合物的理化性质如下：
无色油状物；收率为79％；该化合物的结构表征：1H NMR(600MHz,Chloroform-d)δ7.44(d,J＝1.8Hz,2H),7.37(d,J＝1.8Hz,1H),7.09(d,J＝8.2Hz,1H),6.96(d,J＝2.4Hz,1H),6.93(dd,J＝8.3,2.3Hz,1H),6.06(s,1H),5.73(s,1H),2.25(s,3H),2.24(s,3H)；HRMS(ESI)calcd for C18H15O3Cl2F2[M+HCOO]-:387.0361,found 387.0371.
化合物18.1-((2-(3,5-二氯苯基)-1,1-二氟烯丙基)氧基)-3-乙基-2-甲氧基苯
该化合物的理化性质如下：
无色油状物；收率为70％；该化合物的结构表征：1H NMR(600MHz,Chloroform-d)δ7.62(s,2H),7.35(s,1H),7.17(d,J＝8.1Hz,1H),6.78(s,1H),6.74(d,J＝8.1Hz,1H),6.06(s,1H),5.78(s,1H),3.86(s,3H),2.63(q,J＝7.4Hz,2H),1.24(t,J＝7.6Hz,3H).HRMS(ESI)calcd for C18H16O2Cl2F2Na[M+Na]+:395.0393,found 395.0377.
化合物19.1,3-二氯-5-(3-(4-叔丁基苯氧基)-3,3-二氟丙-1-烯-2-基)苯
该化合物的理化性质如下：
无色油状物；收率为78％；该化合物的结构表征：1H NMR(600MHz,Chloroform-d)δ7.48(d,J＝1.7Hz,2H),7.40(d,J＝8.5Hz,3H),7.15(d,J＝8.6Hz,2H),6.11(s,1H),5.78(s,1H),1.36(s,9H)HRMS(ESI)calcd for C19H17OCl2F2[M-H]-:369.0625,found 369.0642.
化合物20.1,3-二氯-5-(3-(2-叔丁基苯氧基)-3,3-二氟丙-1-烯-2-基)苯
该化合物的理化性质如下：
无色油状物；收率为68％；该化合物的结构表征：1H NMR(600MHz,Chloroform-d)δ7.46(d,J＝8.2Hz,1H),7.42(s,2H),7.35(d,J＝8.5Hz,2H),7.20(t,J＝7.7Hz,1H),7.11(t,J＝7.5Hz,1H),6.07(s,1H),5.74(s,1H),1.23(s,9H)；HRMS(ESI)calcd forC19H19OCl2F2[M+H]+:371.0078,found 371.0774.
化合物21.1,3-二氯-5-(3-(2-甲氧基苯氧基)-3,3-二氟丙-1-烯-2-基)苯
该化合物的理化性质如下：
无色油状物；收率为76％；该化合物的结构表征：1H NMR(600MHz,Chloroform-d)δ7.68(d,J＝1.7Hz,2H),7.40(t,J＝1.8Hz,1H),7.36–7.33(m,1H),7.27–7.22(m,1H),7.00(dd,J＝8.2,1.1Hz,1H),6.97(td,J＝7.9,1.3Hz,1H),6.13(s,1H),5.83(s,1H),3.91(s,3H)；HRMS(ESI)calcd for C16H12O2Cl2F2Na[M+Na]+:367.0080,found 367.0064.
化合物22.1,3-二氯-5-(3-(3-甲氧基苯氧基)-3,3-二氟丙-1-烯-2-基)苯
该化合物的理化性质如下：
无色油状物；收率为70％；该化合物的结构表征：1H NMR(600MHz,Chloroform-d)δ7.42(d,J＝1.6Hz,2H),7.36(t,J＝1.8Hz,1H),7.25–7.22(m,1H),6.78(t,J＝9.3Hz,2H),6.72(s,1H),6.06(s,1H),5.74(s,1H),3.79(s,3H)HRMS(ESI)calcd for C16H12O2Cl2F2Na[M+Na]+:367.0080,found 367.0078.
化合物23.1,3-二氯-5-(3-(4-甲氧基苯氧基)-3,3-二氟丙-1-烯-2-基)苯
该化合物的理化性质如下：
无色油状物；收率为68％；该化合物的结构表征：1H NMR(600MHz,Chloroform-d)δ7.43(s,2H),7.37(s,1H),7.10(d,J＝8.5Hz,2H),6.86(d,J＝8.8Hz,2H),6.05(s,1H),5.73(s,1H),3.79(s,3H)；HRMS(ESI)calcd for C16H13O2Cl2F2[M+H]+:345.0261,found345.0241.
化合物24.(4-((2-(3,5-二氯苯基)-1,1-二氟烯丙基)氧基)-2-甲基苯基)(甲基)硫烷
该化合物的理化性质如下：
无色油状物；收率为58％；该化合物的结构表征：1H NMR(600MHz,Chloroform-d)δ7.46(s,2H),7.40(s,1H),7.16(d,J＝8.5Hz,1H),7.06(d,J＝8.6Hz,1H),7.02(s,1H),6.09(s,1H),5.77(s,1H),2.48(s,3H),2.37(s,3H)HRMS(ESI)calcd for C17H13OCl2F2S[M-H]-:373.0032,found 373.0048.
化合物25.1,2-二氯-4-((2-(3,5-二氯苯基)-1,1-二氟烯丙基)氧基)苯
该化合物的理化性质如下：
无色油状物；收率为54％；该化合物的结构表征：1H NMR(600MHz,Chloroform-d)δ7.39(d,J＝10.8Hz,4H),7.31(s,1H),7.05(s,1H),6.06(s,1H),5.76(s,1H)HRMS(ESI)calcd for C15H7OCl4F2[M-H]-:380.9214,found 380.9236.
化合物26.2-(2-(3,5-二氯苯基)-1,1-二氟烯丙基)-1-异丙基-4-甲苯
该化合物的理化性质如下：
无色油状物；收率为81％；该化合物的结构表征：1H NMR(600MHz,Chloroform-d)δ7.44–7.41(m,2H),7.38(s,1H),7.17(d,J＝7.9Hz,1H),7.11(s,1H),7.02(d,J＝7.8Hz,1H),6.10(s,1H),5.72(s,1H),3.05(hept,J＝7.0Hz,1H),2.33(s,3H),1.13(d,J＝6.9Hz,6H)；HRMS(ESI)calcd for C19H18Cl2F2ONa[M+Na]+:393.0595,found 393.0606.
本发明要解决的第二个技术问题是提供上述化合物在制备农用杀虫剂的用途。
活性试验例1：目标化合物室内小菜蛾活性测定。
采用采用浸叶法：将目标化合物溶解在DMSO中，供试昆虫是小菜蛾2龄幼虫，为室内正常饲养的正常群体，用镊子浸渍甘蓝叶片于已配置好的溶液中10-15秒，取出后自然晾干，待药液干后，放入垫有滤纸的直径为10cm的培养皿中，接入2龄小菜蛾幼虫，每皿20头，然后盖好盖子，置于温度为26℃、相对湿度为75％的培养箱中，48小时后观察试验结果，每组药液设置三个平行。
48小时后观察并统计实验组和对照组小菜蛾的死亡情况，用毛笔轻触虫体，没有明显反应视为死亡。
根据下列公式计算试虫48h的死亡率(％)及校正死亡率(％)。
Figure BDA0004060289660000131
Figure BDA0004060289660000132
活性试验例2：目标化合物室内玉米螟活性测定。
采用人工饲料混毒法：将目标化合物溶解在DMSO中，得到浓度为1mg/mL的药液待用。取药液2ml加入配制好的18g饲料中，搅拌混匀，倒入灭菌的培养皿中，并用小刀将饲料中部按“井”字形切割，把饲料中心形成的方块饲料挑起，以便于玉米螟幼虫的取食和栖息。选取大小一致的3龄幼虫接入“井”字中，每皿20头，对照为在饲料中加入等量溶剂。重复3次。用保鲜膜封好，置于温度为26℃、相对湿度为75％的培养箱中，分别于48h和72h后检查死、活虫数(以毛笔尖触动虫体，不动者为死亡)。根据下列公式计算试虫48h的死亡率(％)及校正死亡率(％)。
Figure BDA0004060289660000141
Figure BDA0004060289660000142
活性试验例3：目标化合物室内草地贪夜蛾活性测定。
采用人工饲料混毒法：将目标化合物溶解在DMSO中，得到浓度为1mg/mL的药液待用。取药液2ml加入配制好的18g饲料中，搅拌混匀，平均加入到灭菌的24孔板中，每孔放一头虫子，12头为一个处理，每个处理重复3次。对照为在饲料中加入等量溶剂。用保鲜膜封好，置于温度为26℃、相对湿度为75％的培养箱中，检查48h后活虫数(以毛笔尖触动虫体，不动者为死亡)。根据下列公式计算试虫48h的死亡率(％)及校正死亡率(％)。
Figure BDA0004060289660000143
Figure BDA0004060289660000144
活性试验例4：目标化合物室内朱砂叶螨活性测定。
采用玻片浸渍法：分别称取2mg供试化合物，用200μL丙酮溶解，再用配好的1‰吐温80 定容至20mL，即配置成100μg/mL药液待用。将1cm宽的双面胶的贴在载玻片的一端，用0号毛笔挑选健康活泼、螨龄一致的朱砂叶螨雌成螨，小心整齐地将其背部粘在双面胶上，每块玻片粘30头左右，排成2行，将粘有供试螨的玻片放在垫有湿润海绵的铁盘中，并将铁盘置于26±1℃、相对湿度60％～80％、光照L:D＝14h:10h条件下的光照培养箱中，放置4小时后，用体视显微镜检查，剔除死亡和不活泼的个体，记录每块玻片上的活螨数量。将载玻片粘有螨的一端在供试药液中振荡浸渍5s后取出，用小滤纸条小心吸去多余药液后放回铁盘，置于相同饲养条件下光照培养箱中，一块玻片为一个处理，每处理重复3次，以1‰吐温80溶液为空白对照。浸药处理24h后将玻片取出在体视显微镜下检查结果，检查时用毛笔尖轻触螨体，以其螯肢不动者为死亡，记录死亡个体数；连续观察记录72h。根据下列公式计算供试螨48h和72h的死亡率(％)及校正死亡率(％)。
Figure BDA0004060289660000145
Figure BDA0004060289660000146
结论
活性测试表明，在0.5mg/mL浓度时化合物1-4，6-8，10-12和14对小菜蛾表现出100％致死率，化合物1，3，4，7，11，13，14对玉米螟表现出100％致死率，化合物7和14对草地贪夜蛾致死率为100％。
其中化合物7，12及14在10ug/mL时对小菜蛾致死率为100％；对玉米螟致死率为100％，80％及100％；对草地贪夜蛾致死率分别为100％，45％及100％。
二氟烯烃醚类化合物16-26在0.5mg/mL浓度下对朱砂叶螨杀虫活性大于80％。
鉴于此，本发明公开的一种二氟烯烃醚和肟醚类衍生物杀虫/螨活性显著，今后有望用于制备新型高效杀虫/螨剂。
以上所述，仅是本发明的较佳实施例而己，并非对本发明作任何形式上的限制，任何未脱离本发明技术方案内容，依据本发明的技术实质对以上实施例所作的任何简单修改、等同变化与修饰，均仍属于本发明技术方案的范围内。

Claims (10)

1.二氟烯烃醚和肟醚类衍生物，其特征在于，该系列衍生物的结构通式如式(I)和(II)所示：
Figure FDA0004060289650000011
式(I)和(II)中，Ar为独立地选自任意取代或未取代的芳基、任意取代或未取代的杂芳基中的一个或多个芳基；
R为独立地选自任意取代或未取代的烷基、任意取代或未取代的烷氧基、任意取代或未取代的芳基、任意取代或未取代的杂芳基中的一个或多个；
R1独立地选自腈基、硝基、任意取代或未取代的烷基、任意取代或未取代的烷氧基、任意取代或未取代的芳基、任意取代或未取代的杂芳基中的一个或多个；
R2独立地选自腈基、硝基、任意取代或未取代的烷基、任意取代或未取代的烷氧基、任意取代或未取代的芳基、任意取代或未取代的杂芳基中的一个或多个；
R3独立地选自任意取代或未取代的烷基、任意取代或未取代的烷氧基、任意取代或未取代的芳基、任意取代或未取代的杂芳基中的一个或多个。
2.如权利要求1所述的二氟烯烃醚和肟醚类衍生物，其特征在于：
Ar为独立地选自任意取代或未取代的C5-C6芳基、任意取代或未取代的C5-C6杂芳基中的一个或多个；
R为独立地选自任意取代或未取代的C5-C6芳基、任意取代或未取代的C5-C6杂芳基中的一个或多个；
R1独立地选自腈基、硝基、任意取代或未取代的C1-C6烷基、任意取代或未取代的C1-C6烷氧基、任意取代或未取代的C5-C6芳基、任意取代或未取代的C5-C6杂芳基中的一个或多个；
R2独立地选自腈基、硝基、任意取代或未取代的C1-C6烷基、任意取代或未取代的C1-C6烷氧基、任意取代或未取代的C5-C6芳基、任意取代或未取代的C5-C6杂芳基中的一个或多个；
R3独立地选自任意取代或未取代的C1-C6烷基、任意取代或未取代的C1-C6烷氧基、任意取代或未取代的C5-C6芳基、任意取代或未取代的C5-C6杂芳基中的一个或多个；
所述取代指的是任选被卤素、硝基、氰基、羟基、胺基、巯基、C1-C6烷基中的一个或多个取代；
优选地，Ar独立地选自苯基、苄基、吡啶基、吡唑基、吡咯基、呋喃基、噻唑基、苯并吡咯基中的一个或多个；
R独立地选自苯基、苄基、吡啶基、吡唑基、吡咯基、呋喃基、噻唑基、苯并吡咯基中的一个或多个；
R1独立地选自甲基、乙基、正丙基、正丁基、仲丁基、异丁基、苯基、苄基、吡啶基、吡唑基、吡咯基、呋喃基、噻唑基、苯并吡咯基、哒嗪、嘧啶、吡嗪、-CN、-NO2、-CH2CN、-CH2CH2CN、CH2CH2CN、CHCNCH3、CH2CH2CH2CN、CH2CHCNCH3、CHCNCH2CH3、
Figure FDA0004060289650000021
R2独立地选自甲基、乙基、正丙基、正丁基、仲丁基、异丁基、苯基、苄基、吡啶基、吡唑基、吡咯基、呋喃基、噻唑基、苯并吡咯基、哒嗪、嘧啶、吡嗪、-CN、-NO2、-CH2CN、-CH2CH2CN、CH2CH2CN、CHCNCH3、CH2CH2CH2CN、CH2CHCNCH3、CHCNCH2CH3、
Figure FDA0004060289650000022
R3独立地选自甲基、乙基、正丙基、正丁基、仲丁基、异丁基、苯基、苄基、吡啶基、吡唑基、吡咯基、呋喃基、噻唑基、苯并吡咯基中的一个或多个。
3.根据权利要就1所述的二氟烯烃醚和肟醚类衍生物，其特征在于选自下述具体化合物：
(1)R1＝4-溴苯基，R2＝甲基，R3＝3,5-二氯苯基；
(2)R1＝4-碘苯基，R2＝甲基，R3＝3,5-二氯苯基；
(3)R1＝2,6-二氟苯基，R2＝甲基，R3＝3,5-二氯苯基；
(4)R1＝2-溴,4-氟苯基，R2＝甲基，R3＝3,5-二氯苯基；
(5)R1＝3-三氟甲基苯基，R2＝甲基，R3＝3,5-二氯苯基；
(6)R1＝3-甲基-4氟苯基，R2＝甲基，R3＝3,5-二氯苯基；
(7)R1＝α-呋喃基，R2＝甲基，R3＝3,5-二氯苯基；
(8)R1＝β-萘基，R2＝甲基，R3＝3,5-二氯苯基；
(9)R1＝3,4-(亚甲基二氧)苯基，R2＝甲基，R3＝3,5-二氯苯基；
(10)R1＝2-(1-甲基)吡咯基，R2＝甲基，R3＝3,5-二氯苯基；
(11)R1＝3-苯氧基苯基，R2＝甲基，R3＝3,5-二氯苯基；
(12)R1＝2-噻吩基，R2＝甲基，R3＝3,5-二氯苯基；
(13)
Figure FDA0004060289650000023
R3＝3,5-二氯苯基；
(14)R＝3,5-二氯苯基，Ar＝苯基；
(15)R＝3,5-二氯苯基，Ar＝3,4-二甲基苯基；
(16)R＝3,5-二氯苯基，Ar＝4-乙基-2-甲氧基苯基；
(17)R＝3,5-二氯苯基，Ar＝4-叔丁基苯基；
(18)R＝3,5-二氯苯基，Ar＝2-叔丁基苯基；
(19)R＝3,5-二氯苯基，Ar＝2-甲氧基苯基；
(20)R＝3,5-二氯苯基，Ar＝3-甲氧基苯基；
(21)R＝3,5-二氯苯基，Ar＝4-甲氧基苯基；
(22)R＝3,5-二氯苯基，Ar＝3-甲基-4-甲硫基苯基；
(23)R＝3,5-二氯苯基，Ar＝3,4-二氯苯基；
(24)R＝3,5-二氯苯基，Ar＝5-甲基-2-异丙基苯基。
4.如权利要求1、2、3所述的二氟烯烃肟醚类衍生物的制备方法，其特征在于，所述制备方法，其特征在与包括下述步骤：
步骤1，以系列酮类化合物
Figure FDA0004060289650000031
为原料，与盐酸羟胺反应值得肟类中间体
Figure FDA0004060289650000032
步骤2，系列肟类中间体
Figure FDA0004060289650000033
与三氟甲基烯烃类化合物
Figure FDA0004060289650000034
反应，制备得到式(II)所示化合物。
5.如权利要求1、2、3所述的二氟烯烃醚类衍生物的制备方法，其特征在于，所述制备方法，其特征在与包括下述步骤：
系列酚与三氟甲基烯烃类化合物
Figure FDA0004060289650000035
反应，制备得到式(I)所示化合物。
6.如权利要求书4所述的二氟烯烃肟醚类衍生物制备方法，其特征在于，步骤1反应溶剂选自N,N-二甲基甲酰胺、N,N-二乙基甲酰胺、1，4-二氧六环、四氢呋喃、甲苯、乙酸乙酯、二甲基亚砜、甲醇、乙醇、乙腈、丙酮、水中的一种或几种，反应温度为25～80℃。
7.如权利要求书4所述的二氟烯烃肟醚类衍生物制备方法，其特征在于，所述的酮类化合物
Figure FDA0004060289650000036
选自4-溴苯乙酮、4-碘苯乙酮、2,6-二氟苯乙酮、2-溴,4-氟苯乙酮、3-三氟甲基苯乙酮、3-甲基-4氟苯乙酮、2-呋喃基甲基甲酮、2-萘乙酮、3,4-(亚甲基二氧)苯乙酮、2-乙酰基-1-甲基吡咯、3-苯氧基苯乙酮、2-噻吩基甲基甲酮、4-二氢色原酮的一种；步骤2反应溶剂为N,N-二甲基甲酰胺、二甲基亚砜、甲苯、二甲苯中的一种或几种，反应温度为60-120℃。
8.如权利要求书4所述的二氟烯烃肟醚类衍生物制备方法，其特征在于，步骤2所述的化合物
Figure FDA0004060289650000037
为1,3-二氯-5-(1-三氟甲基-乙烯基)苯；反应溶剂选自N,N-二甲基甲酰胺、N,N-二乙基甲酰胺、1，4-二氧六环、四氢呋喃、甲苯、乙酸乙酯、二甲基亚砜、甲醇、乙醇、乙腈、丙酮、水中的一种或几种，反应温度为25～90℃。
9.如权利要求4、5、6、7、8、9、10所述的二氟烯烃醚和肟醚类衍生物的制备方法制备的二氟烯烃醚和肟醚类衍生物用于制备杀虫剂的应用。
10.如权利要求4、5、6、7、8、9、10所述的二氟烯烃醚和肟醚类衍生物的制备方法制备的二氟烯烃醚和肟醚类衍生物用于制备杀螨剂的应用。
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109651191A (zh) * 2019-01-07 2019-04-19 华南理工大学 一种二氟甲基肟醚衍生物及其合成方法
CN114644539A (zh) * 2022-04-01 2022-06-21 安徽农业大学 一种含烯烃的二氟芳氧醚的合成方法及其在农药中的用途

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109651191A (zh) * 2019-01-07 2019-04-19 华南理工大学 一种二氟甲基肟醚衍生物及其合成方法
CN114644539A (zh) * 2022-04-01 2022-06-21 安徽农业大学 一种含烯烃的二氟芳氧醚的合成方法及其在农药中的用途

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
HAO ZENG等: "Single C(sp3)−F Bond Activation in a CF3 Group: Ipso-Defluorooxylation of (Trifluoromethyl)alkenes with Oximes", ORG. LETT., vol. 21, 25 January 2019 (2019-01-25), pages 1130 *
HAO ZENG等: "Three component hydroxyletherification and hydroxylazidation of (trifluoromethyl)alkenes:access to a-trifluoromethyl b-heteroatom substituted tertiary alcohols", CHEM. COMMUN., vol. 56, 29 April 2020 (2020-04-29), pages 6241 - 6244 *
QINGQIANG TIAN等: "Selective C−F Bond Etherification of Trifluoromethylalkenes with Phenols", J. ORG. CHEM., vol. 87, 9 August 2022 (2022-08-09), pages 10908 *

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